Foamed polyester resin laminated products and method of making same



9 1965 c. 1.. WILSON ETAL 3, 7 3

FOAMED POLYESTER RESIN LAMINATED PRODUCTS AND METHOD OF MAKING SAMEFiled July 8. 1954 INV N 0R8 CHE/5 ram/ikfnzz 50M"; 0564? SHUFFMIA/firromvey disintegrates.

United States Patent V 3,170,832 FOAMED POLYESTER RESIN LAMINATED PROD-UCTS AND METHOD OF MAKING SAME Christopher L. Wilson,-Cranberry Lake,Sloatsburg, and Oscar Shulfman, Yonkers, N.Y., assignors to Hudson FoamPlastics Corporation, Edgewater, NJ., a corporation of New York FiledJulyS, 1954, Ser; No. 441,984 4 Claims. (Cl. 161-119) The presentinvention relates to novel laminated prod ucts and, more particularly,to laminated products comprising one or more layers of foamed polyesterresins united with one or more layers of another material.

Many different types of polyester resins, made by ester-. ifyingpolycarboxylic acids with polyhydric alcohols, are known. These resinshave been cast or extruded to form filmsythey'have' been molded intoshaped products, used as coating and impregnating materials, etc. Morerecently, a method of converting certain of these resins into lightweight, expanded or foamed materials has been disclosed and claimed in acopending patent application, Serial No. 420,744, filed April 2, 1954,by Christopher L. Wilson and Oscar Shuifman, now US. Patent No.2,961,418. In the referred-to patent application one method of makingthe foamed resin product is to take a polyester resin which is areaction product of adipic acid and diethylene glycol, said resin havingan acid number between about 0 and 20 and a hydroxyl number of-betweenabout 20 and 100, mix the resin with a mixture of "ice . with referenceto the accompanying drawing wherein like parts are designated with thesame numbers.

FIG. 1.is a perspective view of one form of laminated material of thepresent invention with a portion of one layer thereof turned back uponitself. 1

FIG. 2 is a perspective view of another embodiment of a material of thepresent invention.

FIG. 3 is an elevation cross sectional view illustrating one step in themanufacture of one type of laminated article made in accordance with thepresent invention.

FIG. 4 is a partial perspective view of the article made in accordancewith the process illustrated in FIG. 3.

FIG. 5 is a perspective view of another type of laminated article madein accordance with the present invention.

FIG. 6 is a cross section elevation view illustrating a step ina moldingprocess in accordance with the present toluene di-isocyanate-2,4 and2,6, a small amount of water and a tertiary amine catalyst, and permitthe reaction which results to proceed so that a light weight resilient,foamed product is formed.

All of'the foamed products made as described in the above referred topatentapplication of Wilson and Shuffman, as well as any other polyesterfoamed material, can be utilized in thenovel materials of the presentinvention.

Although resilient, foamed polyester resins, made, for example, asdescribed in the Wilson and Shuffman application, have propertiesgenerally similar to those of foam rubber, it has been found that thenew resin materials have many properties which are superior to the foamrubber product.

Foam rubber, for example, cannot be successfully laminated to othermaterials with a sufficiently firm bond to stand the stresses of hardusage. It is inherently too easily torn so that bonds made with anadhesive soon fail. Also, if an attempt is made to heat seal a layer offoam rubber to another thermoplastic material, the foam rubber Thus,even though foam rubber has been found to be highly successful incushioning and general upholstering, it has not been able to besuccessfully adapted to many other usese that are indicated for amaterial having the resiliency and softness possessed by foam rubber. a

One object of the present invention is to provide novel laminatedmaterials made from foamed polyester resins.

Another object of the invention is to'provide novel upholsteringmaterials.

Another object of the invention is to provide improved cushioningmaterials of laminated construction.

Another object of the invention is to provide novel laminated materialscomprising one or more layers of an expanded, resilient material and one'or more layers of a film-forming thermoplastic resinous material.

A further object is to provide methods of making improved laminatedamterials including resilient, expanded materials.

The invention will now be described in more detail invention.

FIG. 7 is a cross sectional elevation view of still another type oflaminated article of the present invention.

A feature of the invention is the provision of novel laminated materialshaving many new commercial uses, comprising one or more layers offoamed, expanded, low density polyester resin firmly united to one ormore layers of other materials.

In accordance with the present invention it has been found that foamedpolyester resins have properties which enable them to be joined tosurfaces of many other materials such as sheets or films ofthermoplastic resinous materials such as polyvinylchloride,'polyethylene, other polyester resins, natural and syntheticrubbers, cellulose acetate, cellulose nitrate, polystyrene, otherpolyvinyl Wilson et al. application and a sheet of polyvinyl chloridecan be made as follows. Referring to FIG. 1, one sur- -face 2 of a sheet4 of the foamed resinousmaterial is coated with a film 6 of a polyesterresin in the non- For example,'the resin may be one expanded state. madeby esterifying a dibasic acid such as succinic, adipic, or azelaic acidand a glycol such as di-, tri-, or-polyethylene glycol and then reactedwith a diisocyanate to give an adhesive of regulated curing propertiesand flexibility.

The under surface 8 of the sheet 10' of polyvinyl chloride is coatedwith a film 12 of the same polyester resin. The two coated surfaces arepressed together and permitted to cure at room temperature. The curingprocess takes from a few minutes to several hours depending upon theparticular chemical composition of the adhesive. When completely cured,the two materials will be found to be firmly joined together. Thelaminated article can be flexed and crumpledwithout destroying the bond.

In a similar manner, sheets of the foamed material can be firmly bondedto thin films or sheets of many other flexible synthetic resinousmaterials such as polyethylene, polyester resins, polyurethanes,;othervinyl plastics such as copolymers of vinyl chloride and vinyl acetate,polystyrene, and also to superpolyamides. Using the same bondingtechnique, the foamed material can also be bonded to woven cotton,woolen or synthetic fibre cloth and natural or synthetic rubber.

Laminated articles can also be madecomprising a layer of the foamedpolyester resin and a rigid material such as glass. A sheet of foamedpolyester resin may be bonded to a sheet of glass by coating a surfaceof the sheet of foamed material and a surface of the glass with films ofthe polyester resin-diisocyanate mixture in liquid form as described inthe previous example, placing the coated surfaces together and allowingto cure.

A different type of laminated article comprising a layer of the foamedpolyester resin and a layer of flexible thermoplastic resinous materialcan be made by the following process. Referring now to FIG. 2, a thinsheet 14 of a thermoplastic resinous material, such as polyethylene, isplaced on top of a sheet 16 of the foamed polyester resin with noadhesive between the two layers. This assembly is placed on the lowerplaten 17 of a high frequency dielectric heat sealing machine. The upperplaten of the machine comprising a plurality of metal bars or rods 18arranged in any desired configuration such as shown in FIG. 3, ispressed down into the upper surface of the soft, yielding sandwich untilonly a short distance separates the upper and lower platens. Theassembly of polyethylene sheet and foamed polyester resin layer is thusarranged in a series of convolutions' 20. Current is applied to themachine for about 2 to seconds using about 2 kw. at 27 megacycles, andthe upper platen is raised free. As shown in FIG. 4, the polyethylenesheet has become fused to the layer of foamed resin along the strips 22which were contacted by the lower ends of the metal bars 18 of the upperplaten and the article assumes the regular convoluted appearance shown.Drawing together of the folds of the layer of foamed material causes itto become convoluted on both surfaces. 5 kw. of power can be applied forbriefer periods of time.

It will be apparent that convolutions of almost any desired surfacepattern can be impressed into the material using the method describedabove. For example, the article can be given a quilted appearance.

Laminated material, made as described above, has many uses in theupholstery and cushioning field. The bond produced is extremely toughand, since no stitching is required, durability is greatly enhanced. Anyof the thermoplastic film-forming resinous materials can be bonded tothe foamed polyester resin in the manner described. For example,polyvinyl chloride sheet material bonds even better than polyethylene.

Articles of many different forms and adapted to a variety of uses, canbe made by heat-sealing a sheet of the foamed polyester resin to a sheetof unfoamed therrno plastic resinous material as described above.Referring now to FIG. 5, a sheet 24 of polyvinyl chloride can beheat-sealed around a peripheral edge strip 26 to a layer 28 of thepolyester foam to form a cosmetic applicator.

It is also possible to make laminated articles'of intricate form out ofthe polyester foam, by a molding process.

Referring to FIG. 6, two halves 30a and 30b of a steel mold 32 areprovided with an interior coating layer 34 of uncured polyester resin.The halves of the mold are assembled and the mold'is partially filledwith a'reaction mixture capable of forming the polyester foam asdescribed in aforementioned application Serial No. 420,- 744. Asreaction proceeds in the mixture it expands to fill the mold with thefoamed resin 36. The molded product is then allowed to cure for a periodof time, this period usually being at least one hour. The mold halvesare parted and the laminated article stripped therefrom.

Other resinous materials, such as polyvinyl chloride, can be usedinstead of the polyester resin to coat the interior of the mold. In thiscase the resin coating is in the of (1) a polyester resin derived fromadipic acid and diethylene glycol, (2) toluene diisocyanate, (3) water,and (4) a tertiary amine catalyst; a thermoplastic layer superposed onsaid foamed layer, spaced portions of said foamed layer being compressedand surface portions thereof being directly fused to said thermoplasticlayer.

2. A laminated material comprising a layer of resilient foamed polyesterresin consisting of the'reaction product of (1) a polyester resinderived from a dibasic acid selected from the group consisting ofadipic, succinic and azelaic acids and a glycol selected from the groupconsisting of di-, triand polyethylene glycols, (2) toluenediisocyanate, (3) water, and (4) a tertiary amine catalyst; a layer ofanother material, and the diisocyanate modified polyester resin of saidfirst mentioned layer being fused in situ and bonding opposed areas ofthe layers together at which the first mentioned layer is compressed.

3. A method of making a laminated material comprising superposing alayer of thermoplastic resin on a layer of resilient, foamed polyesterresin consisting of the reaction product of (l) a polyester resinderived from a polycarboxylic acid and a polyhydric alcohol, (2) adiisocyanate, (3) water, and (4) a tertiary amine catalyst; applyingpressure and heat to said superposed layers at predeterminedareas'thereof to heat seal said layers together where said areas aresuperposed and to compress said foamed layer at said areas, andpermitting said heat sealed layers to cool.

4. A laminated material which is the product of the method of claim 3.

References Cited in the file ofthis patent UNITED STATES PATENTS2,121,678 Armor June 21, 1938 2,140,026 Murphy et al. Dec. 13, 19382,376,653 Boyer May 22, 1945 2,409,910 Stober Oct. 22, 1946 2,434,527Untiedt Ian. 13, 1948 2,576,073 Kropa et al. Nov. 20, 1951 2,602,783Simon July 8, 1952 2,621,139 Messing Dec. 9, 1952 2,626,886 Scholl Jan.27, 1953 2,639,252 Simon et al. May 19, 1953 2,642,920 Simon et al. June23, 1953 2,650,212 Windemuth Aug. 25, 1953 2,698,272 Clapp et al. Dec.28, 1954 2,713,884 Schwartz July 26, 1955 FOREIGN PATENTS 516,512Belgium Jan. 15,- 1953

1. A LAMINATED MATERIAL COMPRISING A LAYER OF RESILIENT, FOAMEDPOLYESTER RESIN CONSISTING OF THE REACTION PRODUCT OF (1) A POLYESTERRESIN DERIVED FROM ADIPIC ACID AND DIETHYLENE GLYCOL, (2) TOLUENEDIISOCYANATE, (3) WATER, AND (4) A TERTIARY AMINE CATALYST; ATHERMOPLASTIC LAYER SUPERPOSES ON SAID FOAMED LAYER, SPACED PORTIONS OFSAID FOAMED LAYER BEING COMPRESSED AND SURFACE PORTIONS THEREOF BEINGDIRECTLY FUSED TO SAID THEREMOPLASTIC LAYER.
 3. A METHOD OF MAKING ALAMINATED MATERIAL COMPRISING SUPERPOSING A LAYER OF THERMOPLASTIC RESINON A LAYER OF RESILIENT, FOAMED POLYESTER RESIN CONSISTING OF THEREACTION PRODUCT OF (1) A POLYESTER RESIN DERIVED FROM A POLYCARBOXYLICACID AND A POLYHYDRIC ALCOHOL, (2) A DIISOCYANATE, (3) WATER, AND (4) ATERTIARY AMINE CATALYST; APPLYING PRESSURE AND HEAT TO SAID SUPERPOSEDLAYERS AT PREDETERMINED AREAS THEREOF TO HEAT SEAL SAID LAYERS TOGETHERWHERE SAID AREAS ARE SUPERPOSED AND TO COMPRESS SAID FOAMED LAYER ATSAID AREAS, AND PERMITTING SAID HEAT SEALED LAYERS TO COOL.